The exact forces on classical nuclei in non-adiabatic charge transfer
The exact forces on classical nuclei in non-adiabatic charge transfer
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DOI：
10.1063/1.4908133
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发表时间：
2015-02-28
影响因子：
4.4
通讯作者：
Gross, E. K. U.
中科院分区：
文献类型：
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作者：
Agostini, Federica;Abedi, Ali;Gross, E. K. U.
阿贝迪等人提出的电子和核运动的分解。[物理。莱特牧师。105,123002(2010年)]产生了驱动核运动的随时间变化的势，并完全解释了与电子子系统的耦合。在这里，我们证明了一个独立的经典核轨迹系综在这个精确势能上的传播产生了与模型非绝热电荷转移问题的精确量子动力学本质上没有区别的动力学。指出了在准经典核波包通过两个Born-Oppenheimer曲面的避免交叉点后，精确势场中的阶跃和碰撞特征的重要性，并分析了它们的结构。最后，给出了弹道表面跳跃背景下的精确势的分析，包括速度调节和力诱导的退相干效应的初步研究。(C)2015 AIP出版有限责任公司。
The decomposition of electronic and nuclear motion presented in Abedi et al. [Phys. Rev. Lett. 105, 123002 (2010)] yields a time-dependent potential that drives the nuclear motion and fully accounts for the coupling to the electronic subsystem. Here, we show that propagation of an ensemble of independent classical nuclear trajectories on this exact potential yields dynamics that are essentially indistinguishable from the exact quantum dynamics for a model non-adiabatic charge transfer problem. We point out the importance of step and bump features in the exact potential that are critical in obtaining the correct splitting of the quasiclassical nuclear wave packet in space after it passes through an avoided crossing between two Born-Oppenheimer surfaces and analyze their structure. Finally, an analysis of the exact potentials in the context of trajectory surface hopping is presented, including preliminary investigations of velocity-adjustment and the force-induced decoherence effect. (C) 2015 AIP Publishing LLC.